DE2118241A1 - Polyfluorinated sulfonic acid amines - Google Patents

Description

PATENT ADVOCATE DR HANS-GUNTHIiR EGGERT, DIPLOMA CHEMIST

5 rCIN-LINDEHTHAL PETER-KINT & EN-STRASSE 2 9 1 1 ft 9 A

Cologne, April 14, 1971 Eg / pz / 52

Ugine Kuhlmann, Io rue du General Foy, Paris 8e / France

Polyfluorinated sulfonic acid amine amines

The present invention relates to new industrially useful polyfluorinated amine compounds represented by the general formula _Ώ

■? 1 ^ll 3

are represented in the

CF ₀ , a straight or branched perfluorinated alkyl chain,

η is an integer from 1 to 2o,
a is an integer from 2 to Io and ρ is an integer from O to Io and

R _{1 is} a hydrogen atom, an alkyl radical with 1 to 6 carbon atoms or the radical C_F _O ",., - (CH ^) ₀ -SO ₀ and

η (UiTi. da. c.

R ₀ and R _x denote alkyl radicals having 1 to 6 carbon atoms.

The invention also relates to a method of production of the products represented by the formula (i), which is characterized in that it is a polyfluorinated Reacts sulfonic acid chloride with an amine derivative.

Among the products according to the invention, which consist of at least of a compound of formula (I) are those in which a = 2 or 4 and ρ "is a number between 2 and 6 ^ are particularly interesting.

The polyfluorinated products of the general formula

^ ^R 2 ~ NR ₁ - (CH ₂ ) ^ - N - (i)

can by exposure to polyfluorinated sulfonic acid chlorides

on amine derivatives

^R 2

HN - (CH ₂ ) _p -N (III)

^R 4 S

can be obtained. R ₄ is hydrogen or an alkyl radical with 1 to 6 carbon atoms.

The. Production of polyfluorinated amine derivatives leaves by different from the values for ρ and von Ri, achieve dependent overall reactions.

If ρ <C 3, one obtains independently of R ^ by Ein effect of polyfluorinated sulfonic acid chloride (II) on the amine derivative (ill) a single polyfluorinated Amine derivative according to the reaction:

^C n ^F 2n ₊ 1- < ^CH 2> a- ^S0 2 ^C1

109845/1933

2Ί1824Τ

C.

+ HCl

if p ^^ J and R _{4 is} a hydrogen atom, a mixture of two polyfluorinated amine derivatives is obtained under the same conditions in an unforeseen way according to the reaction: R

H ^'n 3

g'P

^{N + HC1}

When Rj, an alkyl radical of 1 to 6 carbon atoms you always get a single product;

p ^

R ₄ 'R ^

it does not matter which values ρ assumes.

The reactions (1) and (2) take place in one Temperature between 0 and 120 ° C both in the presence and in the absence of a solvent as the reaction medium, The presence of a solvent is generally preferred. The solvent must be behave neutrally towards the reagents under the required reaction conditions. One can e.g. use an ether,

45/1939

■ such as ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, an ester such as ethyl acetate or a hydrocarbon halide, such as chloroform or carbon tetrachloride. The starting products (II) are described above. The polyfluorinated sulfonic acid chlorides (II) are the subject of the French patent application PV I63.587 of August 21, 1960.

w The 'fluorinated compounds of the invention, because of their thermal stability and their surface properties used as surfactants and as dispersants in very different media, for example, mixtures of viscous products such as certain waxes, fats, paints and coatings.

The values given in the table below provide a picture of the interest in the inventive "" the following products:

109845/1939

O ο O in O O · » η OO 0 O vo CVI CVJ

Where

1 1 £ \

O O O

γη m co

ιη

CM

C-

• ι Ε

CU CU CVJ ^. O up ' ¥ O O VO Ί ? T
CVJ CVI S. S. of CVI <—N I. I. ^ r 3 IT} t O Γ I. CVl * f
Ϊ af
Oil CVi cvj O CVJ HO- ³ ο O co 9 Φ 03 co I. public .ρ f ί CVJ I + CVJ -ο af CVJ ο ϋ ο S.
CVJ 1 O & I. I. S. CVJ K) »Λ 0- O I. φ ι- « tH public
O -P Pc ₄ Pci sf
⁷ CV, i orier co r- » I. H O O Ü <♦ - « VO I. iH O Pc ₁ -P tH VO Λ pci O ο vo • Η Ü

1098A5 / 1939

The invention is illustrated below by means of examples explained in more detail. In all examples the yields are given in relation to the fluorinated starting substance.

Example 1 -

Over a period of 15 minutes, 3.5 g of H ₂ N-CH ₂ -CH ₂ -N (CHj) _{2 are added} to a mixture of 12.9 g of C ₁₀ F ₂₁ -CH ₂ -CH ₂ -SO ₂ Cl and loo cnr ethylacetafc. In the course of the addition a white Pestkörper appears, the reaction is exothermic, the temperature rises from 2o to 30 ⁰ C. After addition is complete leaving the reaction medium is 3 hours with stirring itself, which is separated by filtration a solid which twice with 5o cnr of ethyl acetate is washed. The filtrate is captures and removes draw from this the ethyl acetate by longer-lasting Ah under vacuum. In this way you get 11.5 g

₂ .

The reaction yield is 82 %,

Example 2

_{2 g of H 2} N-CH ₂ -CH ₂ -N (CH ^) _{2 are added} to a mixture of Io9.2 g of CgF ₁₇ -CH ₂ -CH ₂ -SO ₂ Cl and 500 cnr of ethyl ether in 1 h 35 min. A white appears as the reaction progresses

Solid, the reaction is exothermic, the temperature

O
The door rises from 20 to 34 C. When the addition is complete, the reaction medium is left to stir for 3 hours, after which 2oo cnr ethyl acetate is added and the resulting mixture is filtered. A solid is separated out in this way and a filtrate is recovered. The latter is subjected to a longer period of removal under vacuum, so that a solid is obtained. This is recrystallized in 400 cnr carbon tetrachloride, 95 * 4 g of a product with a melting point are collected

109845/1939

from 84 to 86 ⁰ C, which has the formula

owns. The reaction yield is

Example 3

In 20 minutes, 5 * 28 g of H ₂ N-CH ₂ -CH ₂ -N (CH,) _{2 are added} to a mixture of 15.22 g of CgF ₁₅ - (CH ₂ -CHg) ₂ -S (Jf ₂ Cl and During the addition, the temperature rises from 22 ° to 35 ° C. and a white solid appears. When the addition is complete, the reaction medium is left to stir for 3 hours cnr Äthylacetet washes the filtrate was recovers and removes the ethyl acetate g by Persistent long evaporation under vacuum from this is obtained in this manner 14.2 of a product having a melting point νώη 54 to 56 ⁰ C, has the following formula..:

The reaction yield is 89 %

Example 4

8.8 g of H ₂ N-CH ₂ -CH ₂ -N (CH ^) _{2 are added} to a

Mixture of 22.3 g of CgF ₁₅ -CH ₂ -CH ₂ -SO ₂ CI and loo cnr ⁵ ethyl ether. In the course of the addition, the temperature rises from 22 to 34 ° C. and a white solid appears. The mixture is then left stirring for 2 hours before being washed four times with 50 cubic meters of water. The organic phase is recovered by decantation and, after removal of the solid, by a longer phase

109845/1939

Stripping off under vacuum gives 23.3 g of a product with a melting point of $ 8 to Jl ⁰ G, which has the following formula:

^C 6 ^F 13-CH ₂ -Ch ₂ -SO ₂ -NH-CH ₂ ^ CH ₂ -N (CH ^) The reaction yield is 93 * 5

Example 5

In 1 hour, 8.8 g of H ₂ N-CH ₂ -CHg-N (CH ^) _{2 are added} to a mixture, heated to 75 ° C., of 22.3 g of CgF ₁₅ -CH ₂ -CH ₂ -SO ₂ Cl and 50 cnr carbon tetrachloride. A white solid appears as the addition progresses. The reaction medium is then left to stand at the specified temperature for 3 hours. Are then added loo cnr ethyl acetate to this mixture and _c washes the resulting solution four times with loo mc? Water. You catch the very dense phase that you mix; anhydrous sodium sulfate dries. After filtering off the sodium sulfate, a filtrate is obtained. The solvents of this filtrate are removed by prolonged stripping in vacuo and 21.8 g of a solid are obtained, more than 95 % of which is C ₆ F ₁₅ -CH ₂ -GH ₂ -So ₂ -NH-CH ₂ -CH ₂ - N (CH ₃ ) ₂ and a small amount of fCgF ^ -CHg-CHg-SOgTg N-CH ₂ -CH ₂ -N (CH, ^. The reaction yield is 88%,

Example 6

In 30 minutes, 17.6 g of HgN-CH ₂ -CH ₂ -N (CH ₅ ) _{2 are added} to a mixture of 24.6 g of C ₂ F ₅ -CH ₂ -CH ₂ -SO ₂ -Cl and 100 cm ⁵ Ethyl ether In the course of the addition, the temperature rises from 20 to 34 ° C. and a white solid appears. The reaction medium is then left to stand with stirring for 3 hours, then a solid is removed by filtration, which is washed twice with 50 cm of ethyl ether. The filtrate is recovered and removed from

10984 5/1939

this the ethyl ether by pulling it off for a longer period of time under vacuum. In this way 26.6 g are obtained.

) ₂ .

The reaction yield is 88 %,

Example 7

In 1 hour, 11.6 g of H ₂ N-CH ₂ -CH ₂ -N (CH,) _{2 are added} to a mixture of 22.3 g of CgF ₁ --CH ₂ -CH ₂ -SO ₂ Cl and 100 cm of ethyl ether . In the course of the addition, the temperature rises from 20 to> 4 ° C. and a white solid appears during the first 30 minutes of the addition and then disappears again. At the end of the addition, the reaction medium is cooled to 20 ° C., the white solid reappearing. The mixture is washed four times with 50 cm of water to dissolve the solid, and the ether phase is collected by decantation. You dry these with; anhydrous sodium sulfate, then the ether is removed by evaporation and a viscous liquid (23 g) of the formula is obtained
C ₆ F ₁ ^ -CH ₂ -CH ₂ -SO ₂ -NH-CH ₂ -Ch -N (C ₂ H ₅ ) ₂ which has a degree of purity of 92 to 95 % . The reaction yield is 86 %,

Example 8

In 30 minutes, add lo.2 g of H ₂ N-CH ₂ -CH ₂ -CH ₂ -N (CH ₃ ) ₂ to a mixture of 22.3 g of CgF ^ -CHg-CHg-SOgCl and loo ethyl ether After the addition, the temperature rises from 22 to 34 ° C. and a white solid appears. The mixture is then left stirring for 2 hours, after which it is washed four times with 50 cubic centimeters of water. The organic base is then recovered by decantation and obtained after evaporation of the solvent

109845/1939

- Io -

22 * 5 g of a pesticide, which consists of 65% _{C 6} P ₁₅ -CH ₂ -CHg-SO ₂

and 35 % off

2N-CH ₂ -CH ₂ -CH ₂ -N (CH ₅ ) ₂ . The reaction yield is 92 $ 0

Example 9

In 1 hour, 22.3 SC ₆ F ₁₅ -CH ₂ -CH ₂ -SO ₂ Cl are added to a mixture of 100 cm of ethyl ether and 26 g of H ₂ N-CH ₂ -CH ₂ -CH ₂ -N (C ₂ H ₅ J ₂ , which is kept at 5 ° C. After the addition is complete, the reaction medium is left to stand for 3 hours with stirring at 5 ° C. The mixture is then washed four times with 50 cnr water and, after decantation, an ether phase is obtained Dries with anhydrous sodium sulfate. The sodium sulfate is removed by filtration and the filtrate is collected. The ether contained in the filtrate is evaporated and 23.8 g of a solid are obtained, which is 70 % of ^C 6 ^P 13 "" ^CH 2 " ^CH 2 " ^S0 2" ^NH " ^CH 2" ^CH 2 " ^CH 2" ^N ^ ^C 2 ^H 5 ^ 2 and 30 % off

N -CH ₂ -CH ₂ -CH ₂ - exists. The reaction yield is 92 %.

Example Io

In 30 minutes, 6.5 g of H ₂ N-CH ₂ -CH ₂ -CH ₂ -OH ₂ - are added to a mixture of 22.3 g of C ₆ F ₁₅ -CH ₂ -CH ₂ -SO ₂ Cl and

100 cm of chloroform, which is kept at 60 ^° C. The reaction medium is then left to stand with stirring ^{at 60 ° C. for 3 hours.} After cooling, a liquid is obtained which is washed four times with 100 cubic centimeters of water.

The organic phase is obtained by decantation

109845/1939

it is dried with anhydrous sodium sulfate. The sodium sulfate is removed by filtration and the filtrate is collected. The chloroform is removed by evaporation and 24.3 g of a solid are obtained, which is 5o % off

, -CH ₂ -CH ₂ -SO ₂ -NH-CH ₂ -CH ₂ -Ch ₂ -N (C ₂ H ₅ ) ₂ and 50 % of F ₁ ^ -CH ₂ -CH ₂ -SoJ- N-CH ₂ -CH ₂ -CH ₂ -N (C ₂ H ₅ ) ₂ .

The reaction yield is 96 %.

109845 / 19.39

Claims (1)

Claims 1. Polyfluorinated sulfonic acid amide amines of the formula in the ^C n ^E> 2n + 1 ^a S ^erad © or branched perfluorinated alkyl chain « η an integer from 1 to 2o « a is an integer from 2 to lo « ρ is an integer between 0 and Io and R. a hydrogen atom, an alkyl radical with 1 to 6 carbon atoms or the radical ^c _n ^P 2n + 1 "" ^ ^CH 2 ^ a " ³ ^ and R ₂ and R 1 represent alkyl radicals having 1 to 6 carbon atoms. " 2. Polyfluorinated sulfonic acid amines according to claim 1 «characterized« that η = 6, 8 or lo «a = 2 or 4« ρ «= 2, R _{1 is} a hydrogen atom and Rg and R are simultaneously methyl or ethyl radicals . j5. Process for the preparation of compounds according to Claim 1 or 2, characterized in that one at temperatures between 0 and 12o ° C a polyfluorinated Sulfonic acid chloride of the formula II R _n ^C n ^P 2n ₊ 1 R ₁ to an amine 1 father of the formula III 109845/1939 < ^CH 2> a- ^S0 2 2> a- ^S0 2 N- (CH ₂ V - N can act. 4. The method according to claim 3, characterized in that «that one works in the presence of an inert solvent. 10984S / 1939